CN102021671B - Macromolecular/ metal composite conductor and manufacture method thereof - Google Patents
Macromolecular/ metal composite conductor and manufacture method thereof Download PDFInfo
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- CN102021671B CN102021671B CN2010106183953A CN201010618395A CN102021671B CN 102021671 B CN102021671 B CN 102021671B CN 2010106183953 A CN2010106183953 A CN 2010106183953A CN 201010618395 A CN201010618395 A CN 201010618395A CN 102021671 B CN102021671 B CN 102021671B
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Abstract
The invention relates to a macromolecular/ metal (metal alloy) composite conductor and a manufacture method thereof. The composite conductor is provided with a skin layer and a core layer, wherein the skin layer is thermoplasticity macromolecular polymer (A), the core layer is a metal alloy (B) with lowi melting point, and the cross section of fiber can be round or irregular. The manufacture method is a complex extrusion method and comprises the steps of preparing a fusant, extruding and postprocessing, wherein a complex extrusion die head is adopted. The composite conductor of the invention has excellent electric conductivity, and the volume specific resistance is 1.0*10<-6>-1.0*100 omega cm. Therefore, the composite conductor can satisfy the requirement on clothes conductors by the clothes industry and can be applied for detective textiles, such as special uniforms, textile soft keyboards, intelligent clothes, intelligent bandages and the like. Because the composite structure of the skin layer and the core layer is adopted, the composite conductor of the invention has excellence in clothes production, has soft handfeel, and can satisfy requirements on color and comfort level by clothes textile in addition to satisfying electric conductivity requirements, and meanwhile, product cost is greatly lowered.
Description
Technical field
The present invention relates to a kind of compound wire, be specifically related to a kind of polymer/metal compound wire, and the preparation method of this compound wire.
Background technology
Along with science and technology development, the development in fields such as space flight, medical treatment has produced higher requirement to the electric conductivity of taking fiber, and is therefore more and more for the developmental research of conducting fibre.Having only metal at present is that the electric conductivity of conductive fiber approaches simple metal, is the best a kind of fiber of electric conductivity, can be used as lead and uses, and is applied to conductive fabric, intelligent clothing.But metal is a conductive fiber also has very important shortcoming, poor such as feel, obvolvent difficulty, and the blending of fiber can not homogenize etc.
Metal is that conductive fiber utilizes the electric conductivity of metal to make.Main method has direct hubbing, and drawing is meant the processing method that under stretching action, lets processed wire rod make its variation in diameter through die channel.The line hubbing is a method of producing metal wire rod usually; But produce the fiber fine rule; Superhard alloy or the repeatedly drawing of adamantine wire drawing die that must successively decrease through the aperture; The cross section compression ratio is little by little at every turn, if once hot candied cross section compression ratio is bigger than normal, hot candied resistance then can surpass the TENSILE STRENGTH of material and cause that this splits.After each wire drawing, all will carry out intermediate annealing, eliminate stress, this has also caused metal fibre to cost an arm and a leg.The boundling hubbing is that many in wire rod producing the single strand drawing method is integrated a branch of, adds the multiple material of bag and carries out drawing again.This method can make the wire drawing number of times reduce significantly, also can prevent the individual filament fracture simultaneously, and present this method is mainly used in produces stainless steel fibre, and the multiple material of external packets is used medium carbon steel, because medium carbon steel and stainless steel have the work hardening of similar tendency.The multifunctional spinnable metallic fibres that a kind of boundling hubbing is made is disclosed among the patent application CN99115236.2, can be with these traditional textile modifications, multifunction, reach antibiotic, antistatic, resisting microwave radiation and effect that some is prevented and cured diseases.Patent ZL200610086041.2 discloses a kind of metal fiber wire and manufacture craft thereof, obtains the metal fiber wire that combination property improves, and adheres for preventing between each root fiber; Scribble materials such as copper; Wire drawing removes with the chemical method cleaning and removing after finishing again, obtains beaming type stainless steel long fiber.Patent ZL98117559.7 discloses a kind of method for preparation of metal bundling long fibre, wherein comprises metal fibre and the separation process that applies separation layer aborning, is employed in to add oxidant in the acid solution that concentration is 3-20% as release agent.
Cutting method is other a kind of method of making metal fibre, is to be raw material with the metal solid, cuts Soft flocks with cutlery.This compares with hubbing, and technology shortens, and is the most easy manufacturing approach of metal fibre, and its cost of manufacture is also lower, still, is difficult to obtain all smooth fibers of one side of cross section.Patent ZL01805441.2 discloses a kind of apparatus and method of metal fibre, and these apparatus and method utilize metallic plate to improve the production efficiency of metal fibre, produce through the cutting of rotating disc blade.
The manufacturing approach of metal fibre also has melt spinning method, and melt spinning is directly to produce metal fibre by motlten metal, and its method has all multi-form; Wherein extrusion by melting is that molten metal is extruded from spinning head with spraying the Quench method; Identical with the basic principle of the method for making of organic fiber and glass fibre, still, molten metal surface tension force is big, viscosity is little; The metal streamline of extruding forms drop easily, so the spinning process difficulty is bigger.
In view of the performance of above-mentioned metal fibre and preparation method's defective, special proposition the present invention.
Summary of the invention
An object of the present invention is to provide a kind of polymer/metal compound wire, the metal composite lead that this compound wire not only has superior electrical conductivity ability, wearability but also has good spinnability satisfies and takes the needs of conduction, and this compound wire cost is lower simultaneously.
Another object of the present invention provides a kind of preparation method of polymer/metal compound wire.
A kind of polymer/metal compound wire provided by the invention; This compound wire is the skin-core structure with cortex and sandwich layer; Wherein, Cortex is a thermoplastic polyester, and sandwich layer is a metal or metal alloy, and the fusing point of described thermoplastic polyester is higher than the fusing point of metal or metal alloy.
The fusing point of described metal or metal alloy is 20～480 ℃.
Described metal comprises gallium, caesium, rubidium, indium, tin, bismuth or cadmium etc., and described metal alloy comprises alloy that above-mentioned two or more metal forms, or the alloy of above-mentioned metal and other element composition.
Described above-mentioned metal is meant the metal that the present invention enumerates out.
Described other element is for forming the metal or the nonmetalloid of metal alloy with metal.Specifically gallium, caesium, rubidium, indium, tin, bismuth, copper, lead, silver, zinc etc. can be comprised, nonmetally silicon etc. can be.
47～450 ℃ of the fusing points of described metal or metal alloy, its more preferably 100-200 ℃.
The fusing point of the metal or metal alloy that compound wire of the present invention is selected for use is low, in the preparation process, can not propose too high unapproachable requirement to extrusion die, satisfies demand of practical production.And preferred low-melting point metal alloy can remedy the bad shortcoming of cold draw property.
Preferably, add metals such as an amount of silver, aluminium in the described metal alloy, can make compound wire trend towards the drawing-off performance of thermoplastic polyester, more can satisfy and take needs.
Described thermoplastic polyester comprises polypropylene, polyester, nylon (PA6), nylon (PA66), polyether-ether-ketone (PEEK), polyphenylene sulfide (PPS) etc.Described polyester comprises PET or PPT.
The fusing point of described thermoplastic polyester is about 150～450 ℃.
Above-mentioned polypropylene, polyester etc. are to take requirement because their processing technology is ripe, satisfied as the cortex of polymer/metal alloy compound wire, environmental friendliness, and low price can be controlled the cost of compound wire.
The cross section of described compound wire can be for circular or special-shaped.
Described cortex, the sandwich layer mass percent in compound wire is: cortex is 72%～98%; Sandwich layer is 2%～28%.
Preferably, the mass percent of sandwich layer is 8%～20%, more preferably 8%～18%.
Selecting for use of the metal alloy of above-mentioned sandwich layer or the quality of metal is the manufacturing technique from the electric conductivity compound wire; Especially from knitting property; The content of metal or metal alloy is lower than at 2% o'clock, and in the fibre forming process, metal alloy is difficult to form the continuity linear structure; Do not reach the favorable conductive effect, can not give full play to its electric conductivity.On the other hand, high 28% o'clock, not only electric conductivity does not have further to improve, because the content of metal or metal alloy increases, and lead adds and man-hour occurs the mobile reduction of thread, spinnability reduces on the contrary.
The fineness of described compound wire is 5～100 μ m.
The conductivity mechanism of polymer/metal alloy compound wire is that the low-melting point metal alloy core causes, therefore, the linear structure of low-melting point metal alloy is continuous more, and electric conductivity is just more excellent.
Among the present invention; Because the physical property that metal alloy and high molecular polymer are not quite similar when the fineness of described compound wire is 5～100 μ m, can make metal alloy and high molecular polymer keep more consistent state; Linear structure is more continuous, and electric conductivity is more excellent.Unstable when the continuity that filament number less than 5 μ m melt extrude, then can not get the durability in the actual use greater than 100 μ m.
The tensile strength of described compound wire is 40MPa～1200MPa.Its preferred 60MPa～1000MPa.
Polymer/metal compound wire tensile strength of the present invention is at 40MPa～1200MPa, and when being lower than 40MPa, fabric intensity does not reach takes requirement.During greater than 1200MPa, compound wire can be because the restriction of the ductility of the metal alloy of sandwich layer be difficult to reach abundant drawing-off, and easy fracture may cause obtaining the durability of electric conductivity.
The percentage elongation of described compound wire is 1%～20%.When percentage elongation less than 1%, be difficult to satisfy the production requirement of back processing such as braiding.Greater than 20% o'clock, the style that is made into fabric can be affected, and limits its Application Areas.
The volume resistivity 1.0 * 10 of described compound wire
-6～1.0 * 10
0Ω cm.
In order to realize another object of the present invention, a kind of manufacturing approach of polymer/metal compound wire is provided, adopt following technical scheme:
(1) thermoplastic polyester fused solution and metal or metal alloy fused solution are passed through compound extrusion die melt extrusion thread;
(2) the melt thread of step (1) being extruded carries out cooling processing, imposes finish thereafter;
(3) it is passed through in heater, heat treatment stretches;
(4) reel with the speed of ultra 800m/min not, promptly get compound wire.
Described compound extrusion die; Comprise cope match-plate pattern and lower bolster, cope match-plate pattern is sheathed in the lower bolster through reference column, forms between reference column and the lower bolster and extrudes micropore; First medium runner in the reference column is in communication with the outside through capillary; Saidly extrude micropore outlet and flush with the extracapillary port, said first medium runner, one end is in communication with the outside through capillary, and the other end enters the mouth with first medium runner and is communicated with; Lower bolster comprises second medium runner, and second medium runner is in communication with the outside through extruding micropore.
Has circle on the lower bolster of described compound extrusion die or abnormity is extruded micropore.
The abnormity is here extruded the cross sectional shape of the compound wire that the shape of micropore can prepare as required and is confirmed.
Thermoplastic polyester fused solution of the present invention is that the raw material thermoplastic polyester is passed through single screw extrusion machine with its fusion; Described metal or metal alloy fused solution is to utilize heating crucible with the metal or metal alloy fusion.Each thermal treatment zone of screw rod, fluid line, measuring pump equitemperature satisfy the melt temperature requirement of thermoplastic polyester fused solution, metal or metal alloy fused solution respectively.
The described cooling processing of step (2) is meant that the melt thread cools off through cooling air, and the temperature of said cooling air is that 20～30 ℃, humidity are 20～60%, the cold air blast velocity 0.4～1m/s of cooling air.Adopt the cooling air of said temperature, humidity, wind speed can obtain that fineness is even, the uniform high-quality compound wire of performance.
Described stretching heat treatment comprises: the compound wire semi-finished product that step (2) obtains are to carry out 1.1～5 times of drawing-offs under 50～250 ℃ in temperature, and then after temperature is to carry out anxiety or relaxation heat setting under 150～350 ℃, obtain the polymer/metal compound wire.
The described thermic devices of step (3) comprises hot-rolling etc.
Step (4) is because there are very big difference in metal and metal alloy thereof and thermoplastic polyester physical property, so reel with the speed that is no more than 800m/min.If adopt speed greater than 800m/min, be prone to cause the continuous structure fracture of sandwich layer metal, the electric conductivity of compound wire descends.
The hot-rolling that passes through of the present invention carries out nervous HEAT SETTING, reels, and makes tension brute force, the percentage elongation of compound wire satisfy the subsequent production requirement.
The invention has the beneficial effects as follows: because the metal and the metal alloy thereof of compound wire sandwich layer of the present invention make its electric conductivity improve greatly than existing conductive fiber, the mode of production is easier than metal fibre.Need can be applied to electric conductivity excellent more special uniform, fabric keyboard, to add heating fabric, to survey in the smart fabric such as fabric.The thermoplastic polyester of cortex has better spinnability, and the protection sandwich layer not by bending, stretch, the infringement when folding, wearing and tearing and washing, thereby it is durable for a long time to keep electric conductivity.In addition, owing to adopt skin-core structure, the production cost of compound wire of the present invention is reduced.
Description of drawings
Fig. 1 is the cross sectional representation of the embodiment of the invention 1
Fig. 2 is the cross sectional representation of the embodiment of the invention 2
The structural representation of Fig. 3 compound extrusion die of the present invention
Wherein: wherein: 1. cope match-plate pattern; 2. lower bolster; 3. stem stem; 4. location structure shoulder; 5. capillary; 6. first medium runner; 7. second medium runner enters the mouth; 8. location structure; 9. second medium runner; 10. extrude micropore
The specific embodiment
The cortex of present embodiment is polyethylene terephtalate (256 ℃ of a fusing point), and sandwich layer is tin bismuth metal alloy (150～180 ℃ of a fusing point), skin/core weight ratio 87: 13.
Raw material and weight proportion according to above-mentioned skin, sandwich layer component are processed to melt through screw extruder, an electric furnace respectively; Be transported to extrusion die through separately melt pipeline again; Two kinds of melts get into same compound extrusion die; And before getting into lower bolster, do not contact mutually by way of separately melt flow channel, the cross section of fiber is realized through the design of extruding micropore.
Distribution plate is positioned at lower bolster top, distribution pin and lower bolster to extrude micropore corresponding one by one.The melt of core component flows into the lower bolster through hole from the centre pipe duct of distribution pin; The skin component is advanced people's guide hole through the slit cross flow of distribution pin lower end; Two components are in contact with one another herein, and the skin component is accomplished the encirclement to core component here, and finally form the cross section of present embodiment.Temperature through cooling air is about 20 ℃, and humidity is about 20%, and cold air blast velocity is about 0.6m/s, imposes finish, reels with the low speed of 800m/min.Through 70 ℃ of hot-rollings, to carry out drawing-off and handle, draw ratio is 3, through 130 ℃ of hot-rollings, carries out nervous HEAT SETTING, reels, and promptly obtains compound wire.Compound wire fineness 17 μ m, tensile strength 820MPa, percentage elongation are 7.5%, are 1.1 * 10 than resistance value
-3Ω cm.
The cross sectional shape of fiber is as shown in Figure 1.
Referring to Fig. 2.On the basis of embodiment 1, the difference of present embodiment is: the cross section of fiber is a trilobal.Compound wire fineness 21 μ m, tensile strength 750MPa, percentage elongation are 7.8%, are 1.0 * 10 than resistance value
-3Ω cm.
On the basis of embodiment 1, the difference of present embodiment is: the compound ratio of skin/core weight 75: 25.Compound wire fineness 17 μ m, tensile strength 820MPa, percentage elongation are 7.2%, are 8 * 10 than resistance value
-4Ω cm.
On the basis of embodiment 1, the difference of present embodiment is: cortex is a polyethylene terephtalate, and sandwich layer is a tin silver metal alloy, the compound ratio of skin/core weight 80: 20.Compound wire fineness 18 μ m, tensile strength 800MPa, percentage elongation are 7.5%, are 9 * 10 than resistance value
-4Ω cm.
Embodiment 5-8
The technological process of embodiment 5-8 is as embodiment 1, and other technological parameters are as seeing the following form 1:
Table 1 embodiment 5-8
Embodiment 9-12
The technological process of embodiment 9-12 is as embodiment 1, and other technological parameters are as seeing the following form 2:
Table 2 embodiment 9-12
Above embodiment is used to explain the present invention, and unrestricted the present invention.Like the selection of cortex thermoplastic polyester, sandwich layer low-melting-point metal or its metal alloy, the variation of the compound ratio of core-skin weight, fiber cross section etc. all belongs to protection scope of the present invention.
Claims (2)
1. polymer/metal compound wire, this compound wire are to have the skin-core structure that cortex and sandwich layer are formed, and cortex is a nylon 66, and fusing point is 250 ℃, and sandwich layer is the rubidium metal, skin/core weight ratio 95: 5;
Raw material and weight proportion according to above-mentioned skin, sandwich layer component are processed to melt through screw extruder, electric furnace respectively; Be transported to extrusion die through separately melt pipeline again; Two kinds of melts get into same compound extrusion die; And before getting into lower bolster, do not contact mutually by way of separately melt flow channel, the cross section of fiber is realized through the design of extruding micropore;
Distribution plate is positioned at lower bolster top, distribution pin and lower bolster to extrude micropore corresponding one by one, the melt of core component flows into the lower bolster through hole from the centre pipe duct of distribution pin, the skin component is passed through the slit cross flow entering guide hole of distribution pin lower end; Two components are in contact with one another herein, and the skin component is accomplished the encirclement to core component here, and finally form required cross section, and the temperature through cooling air is about 20 ℃; Humidity is about 50%, and cold air blast velocity is 0.4m/s, imposes finish, reels with the low speed of 750m/min; Through 100 ℃ of hot-rollings, to carry out drawing-off and handle, draw ratio is 5, through 200 ℃ of hot-rollings; Carry out nervous HEAT SETTING, reel, promptly obtain compound wire, compound wire fineness 15 μ m; Tensile strength 800MPa, percentage elongation are 7.2%, are 12.50 * 10 than resistance value
-6Ω cm.
2. polymer/metal compound wire, this compound wire are to have the skin-core structure that cortex and sandwich layer are formed, and cortex is a poly terephthalic acid ethylene glycol, and fusing point is 265 ℃, and sandwich layer is an aluminium rubidium metal alloy, and fusing point is 227 ℃, skin/core weight ratio 82: 18;
Raw material and weight proportion according to above-mentioned skin, sandwich layer component are processed to melt through screw extruder, electric furnace respectively; Be transported to extrusion die through separately melt pipeline again; Two kinds of melts get into same compound extrusion die; And before getting into lower bolster, do not contact mutually by way of separately melt flow channel, the cross section of fiber is realized through the design of extruding micropore;
Distribution plate is positioned at lower bolster top, distribution pin and lower bolster to extrude micropore corresponding one by one, the melt of core component flows into the lower bolster through hole from the centre pipe duct of distribution pin, the skin component is passed through the slit cross flow entering guide hole of distribution pin lower end; Two components are in contact with one another herein, and the skin component is accomplished the encirclement to core component here, and finally form required cross section, and the temperature through cooling air is about 25 ℃; Humidity is about 35%, and cold air blast velocity is 0.5m/s, imposes finish, reels with the low speed of 700m/min; Through 90 ℃ of hot-rollings, to carry out drawing-off and handle, draw ratio is 3, through 150 ℃ of hot-rollings; Carry out nervous HEAT SETTING, reel, promptly obtain compound wire, compound wire fineness 21 μ m; Tensile strength 925MPa, percentage elongation are 8.5%, are 6.00 * 10 than resistance value
-6Ω cm.
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| KR101917257B1 (en) | 2013-04-12 | 2018-11-09 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Polymer/filler/metal composite fiber and preparation method thereof |
| CN105463834A (en) * | 2016-01-11 | 2016-04-06 | 青岛新维纺织开发有限公司 | Conductive fiber manufacturing method capable of saving metal use amount and improving cladding stability |
| CN111851093A (en) * | 2019-04-30 | 2020-10-30 | 东华大学 | Colored fiber, spinning pack and preparation method thereof |
| CN111850736A (en) * | 2019-04-30 | 2020-10-30 | 东华大学 | Conductive fiber, spinning pack and preparation method thereof |
| CN110227208B (en) * | 2019-06-19 | 2021-06-01 | 华中科技大学 | Flexible fiber electrode coated with polyether-ether-ketone coating, and preparation and application thereof |
| CN114703555A (en) * | 2022-03-07 | 2022-07-05 | 西安工程大学 | One-step forming batch preparation method of core-shell structure liquid metal conductive fiber |
| CN115522280B (en) * | 2022-09-05 | 2024-02-20 | 东华大学 | Method for preparing liquid metal core fiber by using melt spinning |
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| JP2797529B2 (en) * | 1989-10-06 | 1998-09-17 | 東洋紡績株式会社 | Manufacturing method of core-sheath type composite fiber |
| CN1560336A (en) * | 2004-03-10 | 2005-01-05 | 江苏省纺织研究所有限公司 | Fibre of permanent anti-static containing metal oxide and its production process |
| JP2006176940A (en) * | 2004-12-24 | 2006-07-06 | Nippon Ester Co Ltd | Method for producing conductive conjugate fiber |
| CN100412055C (en) * | 2005-08-19 | 2008-08-20 | 华南理工大学 | A organic metal compound production method and antistatic matrix preparation method |
| CN101050555A (en) * | 2007-04-28 | 2007-10-10 | 江苏盛虹化纤有限公司 | Antistatic short fiber |
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